KR100229256B1 - Triazole derivatives and insecticides - Google Patents
Triazole derivatives and insecticides Download PDFInfo
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- KR100229256B1 KR100229256B1 KR1019930002838A KR930002838A KR100229256B1 KR 100229256 B1 KR100229256 B1 KR 100229256B1 KR 1019930002838 A KR1019930002838 A KR 1019930002838A KR 930002838 A KR930002838 A KR 930002838A KR 100229256 B1 KR100229256 B1 KR 100229256B1
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Abstract
살충제용 신규 트리아졸 유도체는 하기 일반식 [I]을 가지며 작물을 피해를 주지 않고 각종 해충, 특히 진딧물을 방제한다.The novel triazole derivatives for insecticides have the following general formula [I] and control various pests, in particular aphids, without damaging the crops.
[상기 식중,[In the above meal,
R1은 저급 알킬기이고;R 1 is a lower alkyl group;
R2및 R3은 동일하거나 상이한 할로겐원자이며;R 2 and R 3 are the same or different halogen atoms;
X는 2-또는 6-위치의 염소원자이다]X is a chlorine atom in the 2- or 6-position]
Description
본 발명은 살충제로 유용한 트리아졸 유도체 및 이것을 활성 성분으로 함유하는 살충제에 관한 것이다.The present invention relates to triazole derivatives useful as insecticides and pesticides containing them as active ingredients.
3-클로로페닐-5-클로로피리딜-1-메틸-1H-1,2,4-트리아졸 등의 트리아졸 유도체는 진드기 및 흡혈층의 방제에 유용하다는 것이 공지되어 있다(RD 278004). 그러나, 이 문헌에서는 상기 유도체의 어떤 농도가 해충의 어떤 종류에 유효한 지에 대한 기술이 없으며 이들 유도체의 근원도 불명확하다. 또한, 상기 문헌에 구체적으로 개시된 화합물은 체계 이동 및 체계 침투가 열등하고 살충제로 만족할 만하다고 거의 말할 수가 없다.It is known that triazole derivatives such as 3-chlorophenyl-5-chloropyridyl-1-methyl-1H-1,2,4-triazole are useful for controlling ticks and blood-sucking layers (RD 278004). However, there is no description in this document of which concentrations of said derivatives are effective for which kind of pests and the origin of these derivatives is unclear. In addition, the compounds specifically disclosed in this document can hardly say that systemic migration and systemic penetration are inferior and satisfactory as pesticides.
농작 원예물에 해를 주는 해충으로는 목화 진딧물, 복숭아혹 진딧물, 싸리수염 진딧물 등의 진딧물류가 있다. 이들 진딧물류는 식물의 생장점을 섭식하여 농원예물에 악영향을 미치며 비루스를 감염시킨다. 따라서, 이들 진딧물류의 방제가 강력히 요망된다. 최근에는 살충제 및 살비제에 대한 저항력이 있는 해충이 발견되어 그 방제가 더욱 심각해졌다. 이런 상황하에, 진딧물류로 대표되는 노린재목 해충의 방제약품은 체계이동 및 체계침투 기능을 가질 것이 요망되고 있다.Pests that harm agricultural horticulture include aphids such as cotton aphids, peach hump aphids, and rhizome aphids. These aphids feed on plant growth, adversely affecting horticulture and infecting viruses. Therefore, the control of these aphids is strongly desired. In recent years, pests resistant to insecticides and acaricides have been found, and their control has become more serious. Under these circumstances, it is desired that the control agent of the stink bugs represented by aphids have the function of system migration and system penetration.
본 발명자들은 상기 해충의 방제에 유용한 살충제를 개발하기 위해 각종 트리아졸 유도체를 합성하여 그 생리활성에 대하여 연구하였다. 결과로, 본 발명자들은 후술되는 일반식 [I]의 화합물이 상기 문헌에 개시된 화합물과 비교할 때 우수한 체계이동 및 체계침투를 가지며 각종 해충 및 진드기에 대해 우수한 살충활성을 나타낸다는 것을 발견하고 본 발명을 완성하였다.The present inventors synthesized various triazole derivatives to develop pesticides useful for controlling the pests, and studied their biological activities. As a result, the present inventors have found that the compounds of the general formula [I] described below have excellent systemic migration and systemic penetration and exhibit excellent pesticidal activity against various pests and mites when compared with the compounds disclosed in the literature. Completed.
본 발명에 따르면 하기 일반식 [I]의 트리아졸 유도체가 제공된다 :According to the present invention there is provided a triazole derivative of the general formula [I]:
[상기 식중,[In the above meal,
R1은 저급 알킬기이고;R 1 is a lower alkyl group;
R2및 R3은 동일하거나 상이한 할로겐 원자이며;R 2 and R 3 are the same or different halogen atoms;
X은 2-또는 6-위치의 염소원자이다]X is a chlorine atom in the 2- or 6-position]
본 발명에 따른 트리아졸 유도체에서 체계 이동 활성 및 체계 침투 활성은 트리아졸 고리의 3-위치에 결합된 벤젠 고리상의 치환기 R2및 R3가 모두 할로겐 원자이기 때문에 특히 향상되는 것이다. 또한, 트리아졸 고리의 1-위치의 알킬 치환기 및 트리아졸 고리의 3-위치에 결합된 벤젠 고리상의 이치환기를 갖는 트리아졸 유도체는 신규 제조방법에 의해 합성될 수 있다.In the triazole derivative according to the present invention, the system shift activity and the system penetration activity are particularly improved because the substituents R 2 and R 3 on the benzene ring bonded to the 3-position of the triazole ring are all halogen atoms. In addition, triazole derivatives having an alkyl substituent at the 1-position of the triazole ring and a disubstituted group on the benzene ring bonded at the 3-position of the triazole ring can be synthesized by a novel preparation method.
일반식 [I]에서 R1의 저급 알킬기로는 메틸기, 에틸기, 프로필기, 이소프로필기, 부틸기, 이소부틸기, t-부틸기, s-부틸기 등이 포함되며, R2및 R3의 할로겐 원자로는 불소, 염소, 브롬 및 요오드가 포함된다. 일반식 [I]의 화합물중 바람직한 것은 식중 R1가 메틸 또는 에틸기이고 X가 2-또는 6-위치의 염소원자인 화합물이다.In general formula [I], the lower alkyl group of R 1 includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, s-butyl group and the like, and R 2 and R 3 Halogen atoms of include fluorine, chlorine, bromine and iodine. Preferred among the compounds of the formula [I] are those compounds wherein R 1 is a methyl or ethyl group and X is a chlorine atom in the 2- or 6-position.
본 발명에 따른 일반식 [I]의 화합물을 표 1에 나타낸다. 또한, 후속 기술에서는 화합물 번호로 언급한다.Table 1 shows the compounds of the general formula [I] according to the invention. In addition, in the following description, reference is made to the compound number.
[표 1]TABLE 1
본 발명에 따른 화합물은 하기 방법에 따라 제조할 수 있으나 이들 방법으로 한정되는 것은 결코 아니다.The compounds according to the invention can be prepared according to the following methods, but are not limited to these methods.
[제조방법 1-1][Manufacturing Method 1-1]
일반식 [I]의 화합물은 일반식 [II]의 알킬 N-아실이미데이트 유도체 또는 알킬 N-아실티오이미데이트 에스테르 유도체를 하기 반응식에 따라 비활성 용매중에서 일반식 [III]의 히드라진 유도체와 반응시킴으로써 수득될 수 있다 :The compound of formula [I] is reacted by reacting an alkyl N-acylimidate derivative or alkyl N-acylthioimide ester derivative of formula [II] with a hydrazine derivative of formula [III] in an inert solvent according to the following scheme. Can be obtained:
[상기 식중,[In the above meal,
Y은 황원자 또는 산소원자이고;Y is a sulfur atom or an oxygen atom;
Z은 저급 알킬기이며;Z is a lower alkyl group;
R1,R2,R3및 X은 상기 정의와 동일하다]R 1 , R 2 , R 3 and X are the same as defined above]
비활성 용매로는 반응에 장해를 주지 않는 용매를 사용할 수 있으며, 메탈올, 에탈올 등의 알콜; 디에틸 에테르, 테트라히드로푸란, 디옥산 디글림 등의 에테르; 펜탄, 헥산, 석유 에테르 등의 지방족 탄화수소; 디클로로메탄, 디클로로에탈, 클로로포름, 사염화탄소 등의 할로겐화 탄화수소; 아세토니트릴 등의 니트릴; N,N-디메틸포름아미드, N,N-디메틸아세트아미드, 디메틸술폭시드, 물 및 그 혼합물이 포함된다. 또한, 히드라진 유도체[III]는 통상 알킬 N-아실이미데이트 유도체 또는 알킬 N-아실티오이미데이트 에스테르 유도체[III] 1 몰당 1~5몰의 양으로 사용된다.As the inert solvent, a solvent which does not interfere with the reaction can be used, and alcohols such as metalol and ethanol; Ethers such as diethyl ether, tetrahydrofuran and dioxane diglyme; Aliphatic hydrocarbons such as pentane, hexane and petroleum ether; Halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride; Nitriles such as acetonitrile; N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, water and mixtures thereof. In addition, the hydrazine derivative [III] is usually used in an amount of 1 to 5 mol per mol of the alkyl N-acylimidadate derivative or the alkyl N-acylthioimidate ester derivative [III].
반응온도는 0℃~사용된 용매의 비점의 범위내에서 임의로 선택되나 바람직한 것은 0~50℃이다. 반응시간은 사용된 출발 화합물에 좌우되나 통상 1~72시간내이다.The reaction temperature is arbitrarily selected within the range of the boiling point of the solvent used 0 ~ 0 ℃ is preferably 0 ~ 50 ℃. The reaction time depends on the starting compound used but is usually within 1 to 72 hours.
이 반응의 구체적인 예는[Synthesis, 483(1983)]에 기재되어 있다.Specific examples of this reaction are described in Synthesis, 483 (1983).
출발 화합물인 알킬 N-아실(티오)이미데이트 유도체[II]는 하기 방법에 따라 제조될 수 있다.Alkyl N-acyl (thio) imidate derivatives [II] as starting compounds can be prepared according to the following method.
[제조방법 1-2][Manufacturing Method 1-2]
일반식 [II]의 알킬 N-아실(티오)이미데이트 유도체는 일반식 [IV]의 벤즈이미데이트 유도체를 하기 반응식에 따라 염기 존재하에 비활성 용매중에서 일반식 [V]의 니코티노일할라이드 유도체와 반응시킴으로써 수득될 수 있다 :Alkyl N-acyl (thio) imidate derivatives of the general formula [II] can be prepared by treating the benzimidate derivative of the general formula [IV] with a nicotinoyl halide derivative of the general formula [V] in an inert solvent in the presence of a base according to the following scheme. It can be obtained by reacting:
[상기 식중,[In the above meal,
W은 할로겐 원자이고;W is a halogen atom;
R2,R3,X,Y 및 Z은 상기 정의와 동일하다]R 2 , R 3 , X, Y and Z are the same as above definition]
또한, 일반식 [IV]의 벤즈이미데이트 유도체는 산 부가염으로 사용될 수 있다. 이 경우에 사불화 붕소, 염화수소, 브롬화 수소, 요오드화 수소 등이 사용될 수 있다.In addition, the benzimidate derivative of the general formula [IV] can be used as an acid addition salt. In this case, boron tetrafluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide and the like can be used.
염기로는 탄산 나트륨, 탄산 칼륨, 탄산수소 나트륨, 수산화 나트륨, 수산화 칼륨 등의 무기 염기; 또는 디에틸아민, 트리에틸아민, 피리딘, 4-N,N-디메틸아미노피리딘 등의 유기 염기를 사용할 수 있다. 용매로는 아세톤, 메틸 에틸 케톤등의 케톤; 디에틸 에테르, 테트라히드로푸란, 디옥산, 디글림 등의 에테르; 벤젠, 톨루엔, 클로로벤젠 등의 방향족 탄화수소, 펜탄, 헥산, 석유 에테르 등의 지방족 탄화수소; 디클로로메탄, 디클로로에탄, 클로로포름, 사염화탄소 등의 할로겐화 탄화수소; 아세트니트릴 등의 니트릴; 디메틸포름아미드, 디메틸아세트아미드, 디메틸술폭시드 및 그 혼합물을 들 수 있다.Examples of the base include inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium hydroxide and potassium hydroxide; Or organic bases such as diethylamine, triethylamine, pyridine and 4-N, N-dimethylaminopyridine. As a solvent, Ketones, such as acetone and methyl ethyl ketone; Ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme; Aliphatic hydrocarbons such as aromatic hydrocarbons such as benzene, toluene and chlorobenzene, pentane, hexane and petroleum ether; Halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride; Nitriles such as acetonitrile; Dimethylformamide, dimethylacetamide, dimethyl sulfoxide and mixtures thereof.
일반적으로 니코티노일할라이드 유도체[V]는 벤즈이미데이트 유도체[IV] 1몰당 0.8~1.3몰의 양으로 사용된다. 염기의 사용량은 벤즈이미데이트 유도체[IV] 1몰단 1.0~2.0몰 당량이다.In general, nicotinoyl halide derivative [V] is used in an amount of 0.8 to 1.3 moles per mole of benzimidate derivative [IV]. The usage-amount of a base is 1.0-2.0 mol equivalent of 1 mol group of benzimidate derivatives [IV].
반응시간은 사용된 출발 화합물에 좌우되나 통상 1~24시간 내이다. 반응온도는 0℃ 내지 사용된 용매의 비점 범위내이다.The reaction time depends on the starting compound used but is usually within 1 to 24 hours. The reaction temperature is in the range of 0 ° C. to the boiling point of the solvent used.
[제조방법 2][Manufacturing Method 2]
본 발명에 따른 일반식 [I]의 화합물은 일반식 [VI]의 N-(페닐술포닐) 벤즈히드라조노일 클로라이드 유도체를 하기 반응식에 따라 루이스산 존재하에 비활성 용매중에서 일반식 [VII]의 3-시아노피리딘 유도체와 반응시킴으로써 수득될 수 있다 :Compounds of the general formula [I] according to the invention are prepared by the reaction of N- (phenylsulfonyl) benzhydrazonoyl chloride derivatives of the general formula [VI] in an inert solvent in the presence of Lewis acid according to It can be obtained by reacting with a cyanopyridine derivative:
[상기 식중,[In the above meal,
R1,R2,R3및 X은 상기 정의와 동일하다]R 1 , R 2 , R 3 and X are the same as defined above]
비활성 용매로는 반응에 장해를 주지 않는 용매를 사용할 수 있으며, 디에틸 에테르, 테트라히드로푸란, 디옥산, 디글림등의 에테르; 벤젠, 톨루엔, 클로로벤젠, 디클로로벤젠 등의 방향족 탄화수소; 펜탄, 헥산, 석유 에테르 등의 지방족 탄화수소; 디클로로메탄, 디클로로에탄, 클로로포름, 사염화탄소 등의 할로겐화 탄화수소; 디메틸포름아미드, 디메틸아세트아미드, 디메틸술폭시드 또는 그 혼합물이 포함된다. 일반적으로 3-시아노피리딘 유도체[VII] 및 루이스산은 N-(페닐술포닐) 벤즈히드라조노일 클로라이드 유도체[VI] 1몰당 1.0~2.0몰의 양으로 사용된다.As the inert solvent, a solvent which does not interfere with the reaction can be used, and ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme; Aromatic hydrocarbons such as benzene, toluene, chlorobenzene and dichlorobenzene; Aliphatic hydrocarbons such as pentane, hexane and petroleum ether; Halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride; Dimethylformamide, dimethylacetamide, dimethyl sulfoxide or mixtures thereof. Generally 3-cyanopyridine derivative [VII] and Lewis acid are used in an amount of 1.0-2.0 mol per mol of N- (phenylsulfonyl) benzhydrazonoyl chloride derivative [VI].
반응온도는 0℃ 내지 사용된 용매의 비점 범위내에서 임의로 선택되나 바람직한 것은 50~150℃ 범위내이다. 반응시간은 사용된 출발 화합물에 좌우되나 통상 30분~5시간 범위내이다.The reaction temperature is optionally selected within the boiling point range of 0 ° C. to the solvent used, but is preferably in the range of 50 ° C. to 150 ° C. The reaction time depends on the starting compound used but is usually in the range of 30 minutes to 5 hours.
이 반응의 구체적인 예는[BULLETIN of the CHEMICAL SOCIETY of JAPAN, vol, 56, pp.545~548(1983)]에 기재되어 있다.Specific examples of this reaction are described in BULLETIN of the CHEMICAL SOCIETY of JAPAN, vol, 56, pp. 545-548 (1983).
[제조방법 3][Manufacturing Method 3]
본 발명에 따른 일반식 [I]의 화합물은 일반식 [VIII]의 N-(페닐술포닐)벤즈아미드라존 유도체를 하기 반응식에 따라 비활성 용매중에서 일반식 [V]의 니코티노일할라이드 유도체와 반응시킴으로써 수득될 수 있다 :Compounds of the general formula [I] according to the present invention are reacted with the nicotinoyl halide derivatives of the general formula [V] in an inert solvent according to the following reaction scheme for the N- (phenylsulfonyl) benzamide razone derivative of the general formula [VIII] It can be obtained by reacting:
[상기 식중,[In the above meal,
R1,R2,R3및 W 및 X은 상기 정의와 동일하다]R 1 , R 2 , R 3 and W and X are the same as above definition]
비활성 용매로는 반응에 장해를 주지 않는 용매를 사용할 수 있으며, 디에틸 에테르, 테트라히드로푸란, 디옥산, 디글림등의 에테르; 벤젠, 톨루엔, 클로로벤젠 등의 방향족 탄화수소; 펜탄, 헥산, 석유 에테르 등의 지방족 탄화수소; 디클로로메탄, 디클로로에탄, 클로로포름, 사염화탄소 등의 할로겐화 탄화수소; 디메틸포름아미드, 디메틸아세트아미드, 디메틸술폭시드 또는 그 혼합물이 포함된다. 일반적으로 니코티노일할라이드 유도체[V]는 N-(페닐술포닐) 벤즈아미드라존 유도체[VIII] 1몰당 1.0~2.0몰의 양으로 사용된다.As the inert solvent, a solvent which does not interfere with the reaction can be used, and ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme; Aromatic hydrocarbons such as benzene, toluene and chlorobenzene; Aliphatic hydrocarbons such as pentane, hexane and petroleum ether; Halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride; Dimethylformamide, dimethylacetamide, dimethyl sulfoxide or mixtures thereof. In general, nicotinoyl halide derivative [V] is used in an amount of 1.0 to 2.0 moles per mole of N- (phenylsulfonyl) benzamide razone derivative [VIII].
반응온도는 0℃ 내지 사용된 용매의 비점 범위내에서 임의로 선택되나 바람직한 것은 50~200℃범위내이다. 반응시간은 사용된 출발 화합물에 좌우되나 통상 30분~5시간 범위내이다.The reaction temperature is arbitrarily selected within the boiling point range of 0 ° C. to the solvent used, but is preferably within the range of 50 ° C. to 200 ° C. The reaction time depends on the starting compound used but is usually in the range of 30 minutes to 5 hours.
이 반응의 구체적인 예는 [BULLETIN of the CHEMICAL SOCIETY of JAPAN, vol. 56, pp.545~548(1983)]에 기재되어 있다.Specific examples of this reaction are described in BULLETIN of the CHEMICAL SOCIETY of JAPAN, vol. 56, pp. 545-548 (1983).
또한, 출발 화합물인 N-(페닐술포닐) 벤즈아미드라존 유도체[VIII]는 하기 방법에 의해 제조될 수 있다.In addition, the starting compound N- (phenylsulfonyl) benzamiderazone derivative [VIII] can be prepared by the following method.
[제조방법 3-2][Manufacturing Method 3-2]
일반식 [VIII]의 N-(페닐술포닐)벤즈아미드라존 유도체는 하기 반응식에 따라 비활성 용매중에서 일반식 [VI]의 N-(페닐술포닐) 벤즈히드라조노일 클로라이드 유도체를 암모니아 기체와 반응시킴으로써 수득될 수 있다 :The N- (phenylsulfonyl) benzamide razone derivative of the general formula [VIII] reacts the N- (phenylsulfonyl) benzhydrazonoyl chloride derivative of the general formula [VI] with an ammonia gas in an inert solvent according to the following scheme. Can be obtained by:
[상기 식중,[In the above meal,
R1,R2및 R3은 상기 정의와 동일하다]R 1 , R 2 and R 3 are the same as above definition
비활성 용매로는 반응에 장해를 주지 않는 용매를 사용할 수 있으며, 디에틸 에테르, 테트라히드로푸란, 디옥산, 디글림등의 에테르; 벤젠, 톨루엔, 클로로벤젠 등의 방향족 탄화수소; 펜탄, 헥산, 석유 에테르 등의 지방족 탄화수소; 디클로로메탄, 디클로로에탄, 클로로포름, 사염화탄소 등의 할로겐화 탄화수소; 디메틸포름아미드, 디메틸아세트아미드, 디메틸술폭시드 또는 그 혼합물이 포함된다. 일반적으로 암모니아 기체는 N-(페닐술포닐) 벤즈히드라조노일 클로라이드 유도체[VI] 1몰당 5.0~10.0몰의 양으로 사용된다.As the inert solvent, a solvent which does not interfere with the reaction can be used, and ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme; Aromatic hydrocarbons such as benzene, toluene and chlorobenzene; Aliphatic hydrocarbons such as pentane, hexane and petroleum ether; Halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride; Dimethylformamide, dimethylacetamide, dimethyl sulfoxide or mixtures thereof. In general, ammonia gas is used in an amount of 5.0 to 10.0 mol per mol of N- (phenylsulfonyl) benzhydrazonoyl chloride derivative [VI].
반응온도는 0℃ 내지 사용된 용매의 비점 범위내에서 임의로 선택되나 바람직한 것은 50~150℃ 범위내이다. 반응시간은 사용된 출발 화합물에 좌우되나 통상 5분~20시간 범위내이다.The reaction temperature is optionally selected within the boiling point range of 0 ° C. to the solvent used, but is preferably in the range of 50 ° C. to 150 ° C. The reaction time depends on the starting compound used but is usually in the range of 5 minutes to 20 hours.
이 반응의 구체적인 예는[BULLETIN of the CHEMICAL SOCIETY of JAPAN, vol, 56, p.547(1983)]에 기재되어 있다.Specific examples of this reaction are described in BULLETIN of the CHEMICAL SOCIETY of JAPAN, vol, 56, p. 547 (1983).
하기 예는 본 발명을 설명하기 위한 것이며 제한하려는 것은 결코 아니다.The following examples are intended to illustrate the invention and are in no way meant to be limiting.
[제조예 1] : 5-(2-클로로피리딘-3-일)-3-(2,6-디플루오로페닐)-1-메틸-1H-1,2,4-트리아졸(화합물 1)Preparation Example 1 5- (2-Chloropyridin-3-yl) -3- (2,6-difluorophenyl) -1-methyl-1H-1,2,4-triazole (Compound 1)
톨루엔 100ml에 에틸-2,6-디플루오로 벤즈이미디데이트 1.9g 및 트리에틸아민1.2g을 용해시키고, 교반하에 5~10℃범위의 온도에서 2-클로로니코티노일 클로라이드 1.8g을 적가한다. 생성 용액을 실온에서 6시간 교반한다. 반응 완료후, 반응용액을 염 수용액으로 세척한 후 물로 세척하여 생성 톨루엔 층을 황산 나트륨으로 건조시킨다.In 100 ml of toluene, 1.9 g of ethyl-2,6-difluorobenzimidate and 1.2 g of triethylamine are dissolved, and 1.8 g of 2-chloronicotinoyl chloride is added dropwise at a temperature ranging from 5 to 10 ° C under stirring. The resulting solution is stirred for 6 hours at room temperature. After completion of the reaction, the reaction solution was washed with aqueous salt solution and then with water to dry the resulting toluene layer with sodium sulfate.
톨루엔 층에 모노메틸 히드라진 0.5g을 가하고 실온에서 8시간 반응시킨다. 반응 완료후, 반응용액을 희석 염산 용액으로 세척한 후 물로 세척하고, 톨루엔 층을 무수 황산 마그네슘으로 건조시키고 감압하에 농축한다. 생성 농축물을 실리카 겔 크로마토그래피(상표명 : Wakogel C-200, 전개용매 : 헥산 및 에틸 아세테이트의 혼액)시켜 목적 황색 과립상 결정 0.8g(수율 25.8%)을 수득한다(융점 167.0~171.0℃)0.5 g of monomethyl hydrazine is added to the toluene layer and allowed to react at room temperature for 8 hours. After completion of the reaction, the reaction solution is washed with dilute hydrochloric acid solution and then with water, the toluene layer is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting concentrate was subjected to silica gel chromatography (trade name: Wakogel C-200, developing solvent: a mixture of hexane and ethyl acetate) to obtain 0.8 g (yield 25.8%) of the desired yellow granular crystals (melting point 167.0 to 171.0 ° C).
NMR데이타 (60 MHz, CDCl3용매, δ가)NMR data (60 MHz, CDCl 3 solvent, δ value)
3.95 (s, 3H)3.95 (s, 3 H)
6.80~7.68 (m, 4H)6.80 ~ 7.68 (m, 4H)
7.95 (dd, 1H)7.95 (dd, 1 H)
8.55 (dd, 1H)8.55 (dd, 1H)
[제조예 2] : 3-(2,6-디클로로페닐)-5-(2-클로로피리딘-3-일)-1-메틸-1H-1,2,4-트리아졸(화합물 3)Preparation Example 2 3- (2,6-dichlorophenyl) -5- (2-chloropyridin-3-yl) -1-methyl-1H-1,2,4-triazole (compound 3)
디클로로벤젠 50ml에 N-메틸-N-페닐술포닐-2,6-디클로로벤조히드라조노일 클로라이드 5.7g 및 2-클로로-3-시아노피리딘 2.3g을 용해시키고, 교반하에 실온에서 무수 염화 알루미늄 2.2g을 가한다. 생성 용액을 유욕으로 120~140℃로 승온시키고 4시간 교반한다. 반응 완료후, 반응용액을 희석 알칼리 용액으로 세척한 후 희석 염산 용액으로 세척한다. 물로 세척한 후, 유기층을 무수 황산 마그네슘으로 건조시키고 감압하에 농축한다. 생성 농축물을 실리카 겔 크로마토그래피(상표명 : Wakogel C-200, 전개용매 : 헥산 및 에틸 아세테이트의 혼액)시켜 목적 담갈색 과립상 결정 1.9g(수율 37.3%)을 수득한다(융점 133.0~135.5℃)In 50 ml of dichlorobenzene, 5.7 g of N-methyl-N-phenylsulfonyl-2,6-dichlorobenzohydrazonoyl chloride and 2.3 g of 2-chloro-3-cyanopyridine are dissolved, and anhydrous aluminum chloride 2.2 is stirred at room temperature with stirring. add g. The resulting solution is heated to 120-140 ° C. with an oil bath and stirred for 4 hours. After completion of the reaction, the reaction solution is washed with dilute alkaline solution and then with dilute hydrochloric acid solution. After washing with water, the organic layer is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting concentrate was subjected to silica gel chromatography (trade name: Wakogel C-200, developing solvent: a mixture of hexane and ethyl acetate) to obtain 1.9 g (yield 37.3%) of the desired pale brown granular crystals (melting point 133.0 to 135.5 ° C).
NMR데이타 (60 MHz, CDCl3용매, δ가)NMR data (60 MHz, CDCl 3 solvent, δ value)
3.93 (s, 3H)3.93 (s, 3 H)
7.30~7.63 (m, 4H)7.30 ~ 7.63 (m, 4H)
7.95 (dd, 1H)7.95 (dd, 1 H)
8.55 (dd, 1H)8.55 (dd, 1H)
[제조예 3] : 3-(2-클로로-6-플루오로페닐)-5-(6-클로로피리딘-3-일)-1-메틸-1H-1,2,4-트리아졸(화합물 7)Preparation Example 3 3- (2-chloro-6-fluorophenyl) -5- (6-chloropyridin-3-yl) -1-methyl-1H-1,2,4-triazole (Compound 7 )
1-메틸-2-피롤리돈(NMP)50ml에 N-메틸 N-페닐술포닐-2-클로로-6-플루오로벤즈아미드라존 8.8g 및 6-클로로니코티노일 클로라이드 4.5g을 용해시킨다. 생성용액을 유욕으로 110~120℃로 승온시키고 2시간 교반한다. 또 170~180℃로 승온시키고 4시간 교반한다. 반응완료후, 클로로포름 200ml을 가하고 물로 세척한다. 생성 유기층을 무수 황산 마그네슘으로 건조시키고 감압하에 농축한다. 생성 농축물은 실리카 겔 크로마토그래피(상표명 : Wakogel C-200, 전개용매 : 헥산 및 에틸 아세테이트의 혼액)시켜 목적 황색 과립상 결정 2.0g(수율 35.5%)을 수득한다(융점 118.5~120.5℃)In 50 ml of 1-methyl-2-pyrrolidone (NMP), 8.8 g of N-methyl N-phenylsulfonyl-2-chloro-6-fluorobenzamide razone and 4.5 g of 6-chloronicotinoyl chloride are dissolved. . The resulting solution is heated to 110-120 ° C. with an oil bath and stirred for 2 hours. Further, the temperature is raised to 170 to 180 ° C. and stirred for 4 hours. After completion of the reaction, 200 ml of chloroform is added and washed with water. The resulting organic layer is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting concentrate was subjected to silica gel chromatography (trade name: Wakogel C-200, developing solvent: a mixture of hexane and ethyl acetate) to obtain 2.0 g (yield 35.5%) of the desired yellow granular crystals (melting point 118.5 to 120.5 ° C).
NMR데이타 (60 MHz, CDCl3용매, δ가)NMR data (60 MHz, CDCl 3 solvent, δ value)
4.03 (s, 3H)4.03 (s, 3 H)
6.83~7.50 (m, 4H)6.83 ~ 7.50 (m, 4H)
8.05 (dd, 1H)8.05 (dd, 1 H)
8.75 (dd, 1H)8.75 (dd, 1 H)
[제조예 4] : 3-(2-클로로-6-플루오로페닐)-5-(6-클로로피리딘-3-일)-1-이소프로필-1H-1,2,4-트리아졸(화합물 11)Preparation Example 4 3- (2-chloro-6-fluorophenyl) -5- (6-chloropyridin-3-yl) -1-isopropyl-1H-1,2,4-triazole (compound 11)
디클로로벤젠 20ml에 N-메틸-N-페닐술포닐-2-클로로-6-플루오로벤조히드라조노일 클로라이드 5.8g 및 6-클로로-3-시아노피리딘 2.3g을 용해시키고, 교반하에 실온에서 무수 염화 알루미늄 2.2g을 가한다. 생성 용액을 유욕으로 140℃로 승온시키고 30분간 교반한다. 반응 완료후, 반응용액을 클로로포름 200ml에 용해시킨다. 클로로포름 용액을 희석 알칼리 용액으로 세척한 후 희석 염산 용액으로 세척한다. 물로 세척한 후 유기층을 무수 황산 마그네슘으로 건조시키고 감압하에 농축한다. 생성 농축물을 실리카 겔 크로마토그래피(상표명 : Wakogel C-200, 전개용매 : 헥산 및 에틸 아세테이트의 혼액)시켜 목적 갈색 점성액 1.0g(수율 18.9%)을 수득한다(굴절율(ND20) : 측정 불가능).In 20 ml of dichlorobenzene, 5.8 g of N-methyl-N-phenylsulfonyl-2-chloro-6-fluorobenzohydrazonoyl chloride and 2.3 g of 6-chloro-3-cyanopyridine were dissolved, and anhydrous at room temperature under stirring. Add 2.2 g of aluminum chloride. The resulting solution is raised to 140 ° C. with an oil bath and stirred for 30 minutes. After the reaction was completed, the reaction solution was dissolved in 200 ml of chloroform. The chloroform solution is washed with dilute alkaline solution followed by dilute hydrochloric acid solution. After washing with water, the organic layer is dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting concentrate was subjected to silica gel chromatography (trade name: Wakogel C-200, developing solvent: a mixture of hexane and ethyl acetate) to obtain 1.0 g (yield 18.9%) of the desired brown viscous liquid (refractive index (N D 20): measurement impossible).
NMR 데이타(60MHz, CDCl3용매, δ가)NMR data (60 MHz, CDCl 3 solvent, δ)
1.60 (d, 6H)1.60 (d, 6H)
4.45~4.95 (m, 1H)4.45-4.95 (m, 1H)
6.95~7.55 (m, 4H)6.95 ~ 7.55 (m, 4H)
7.95 (dd, 1H)7.95 (dd, 1 H)
8.65 (d, 1H)8.65 (d, 1 H)
본 발명에 따른 살충제는 일반식 [I]의 트리아졸 유도체를 활성 성분으로 함유한다.The pesticide according to the present invention contains the triazole derivative of general formula [I] as an active ingredient.
본 발명에 따른 트리아졸 화합물이 살충제용 활성성분으로 사용될 경우, 이들 화합물은 그 자체로 단독으로 사용되거나, 담체, 계면 활성제, 분산제, 보조제 등과 배합되어 분진, 수화성 분말, 에멀션, 미분말, 과립등을 형성할수 있다. 농약 제형용 담체로는 지클라이트, 활석, 벤토나이트, 점토, 카올린, 규조토, 화이트 카본, 질석, 수산화 칼슘, 석영사, 황산 암모늄, 요소등의 고체 담체; 및 이소프로필 알콜, 크실렌, 시클로헥사논, 메틸나프탈렌등의 액체 담체를 들 수 있다. 계면 활성제 및 분산제로는 알킬벤젠 술폰산의 금속염, 디나프틸메탄 디술폰산의 금속염, 알콜의 황산 에스테르, 알킬아릴술포네이트, 리그닌술포네이트, 폴리옥시에틸렌 글리콜 에테르, 폴리옥시에틸렌 알킬아릴 에테르,폴리옥시 에틸렌 소르비탄 모노알킬레이트 등을 들 수 있다. 보조제로는 카르복시메틸셀룰로스, 폴리에틸렌 글리콜, 아라비아 고무 등을 들 수 있다.When the triazole compound according to the present invention is used as an active ingredient for insecticides, these compounds may be used alone or in combination with a carrier, a surfactant, a dispersant, an auxiliary agent, etc. Can form Examples of agrochemical formulation carriers include solid carriers such as zircite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, calcium hydroxide, quartz sand, ammonium sulfate and urea; And liquid carriers such as isopropyl alcohol, xylene, cyclohexanone, methylnaphthalene and the like. Surfactants and dispersants include metal salts of alkylbenzene sulfonic acids, metal salts of dinaphthylmethane disulfonic acids, sulfuric acid esters of alcohols, alkylarylsulfonates, ligninsulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, polyoxy Ethylene sorbitan monoalkylate, etc. are mentioned. Examples of the adjuvant include carboxymethyl cellulose, polyethylene glycol, gum arabic, and the like.
제형시 활성성분의 사용량은 사용목적에 따라 선택될 수 있으나 분진 및 과립의 경우에는 0.05~20중량%, 바람직하게는 0.1~10중량%의 범위내에서 적당하게 선택된다. 에멀션 및 수화성 분말의 경우에는 활성성분이 0.5~80중량%, 바람직하게는 1~60중량%의 범위내에서 적당하게 선택된다.The amount of active ingredient used in the formulation may be selected according to the purpose of use, but in the case of dust and granules, it is appropriately selected within the range of 0.05 to 20% by weight, preferably 0.1 to 10% by weight. In the case of emulsions and water hydratable powders, the active ingredient is suitably selected in the range of 0.5 to 80% by weight, preferably 1 to 60% by weight.
본 발명에 따른 살충제는 줄기 및 잎에 분무되거나 토양에 살포되거나 묘상에 살포되거나 수면 등에 분무되어 사용될 수 있다. 사용시 살충제는 적당한 농도로 희석되어 직접살포 또는 분무된다. 살충제의 살포량은 활성성분으로 사용된 화합물의 종류, 방제될 해충 종류, 충해 경향 및 정도, 환경조건, 사용된 제제 종류 등에 좌우된다. 본 발명에 따른 살충제가 분진 또는 과립으로 직접 사용될 경우 활성성분의 10 아르당 양은 0.05g~5kg, 바람직하게는 0.1~1 kg의 범위내에서 적당하게 선택된다. 또한, 에멀션 또는 수화성 분말로 액체 형태로 사용될 경우 활성성분의 양은 0.1~5000ppm, 바람직하게는 1~1000ppm의 범위내에서 적당하게 선택된다.Pesticides according to the invention can be used by spraying on the stems and leaves, spraying on the soil, spraying on the seedlings, spraying on the surface of water. In use, the pesticide is diluted to a suitable concentration and sprayed or sprayed directly. The amount of application of the pesticide depends on the type of compound used as the active ingredient, the type of pest to be controlled, the tendency and extent of the insecticide, the environmental conditions, the type of the preparation used, and the like. When the pesticide according to the present invention is used directly as dust or granules, the amount of 10 arsaccharides of the active ingredient is suitably selected within the range of 0.05 g to 5 kg, preferably 0.1 to 1 kg. In addition, when used in liquid form as an emulsion or a hydratable powder, the amount of the active ingredient is suitably selected within the range of 0.1 to 5000 ppm, preferably 1 to 1000 ppm.
또한, 본 발명에 따른 살충제는 기타 살충제, 살진균제, 비료, 식물 성장 조절제 등과 혼합 사용될 수 있다.In addition, the pesticide according to the present invention can be used in combination with other insecticides, fungicides, fertilizers, plant growth regulators and the like.
제형법은 이하 대표적인 예를 들어 구체적으로 기술한다. 이 경우에, 화합물 및 첨가제 종류 및 배합비는 이들 예로 제한되지 않으며 광범위하게 변화될 수 있다. 또한, %는 달리 지정되지 않는 한 중량 기준이다.The formulation method is described in detail by way of representative examples below. In this case, the compound and the additive type and the blending ratio are not limited to these examples and can be varied widely. In addition,% is by weight unless otherwise specified.
[제형예 1] : 에멀션Formulation Example 1 Emulsion
화합물 6 30%, 시클로헥사논 20%, 폴리옥시에틸렌 알킬아릴 에테르 11%, 칼슘 알킬벤젠 술포네이트 4% 및 메틸나프탈린 35%을 균일하게 용해시켜 에멀션을 제조한다.An emulsion is prepared by uniformly dissolving Compound 6 30%, cyclohexanone 20%, polyoxyethylene alkylaryl ether 11%, calcium alkylbenzene sulfonate 4% and methylnaphthalin 35%.
[제형예 2] : 수화성 분말Formulation Example 2 Hydration Powder
화합물 3 40%, 규조토 15%, 점토 15%, 화이트 카본 25%, 소듐 디나프틸메탄 디술포네이트 2% 및 소듐 리그닌 술포네이트 3%을 균일하게 혼합 분쇄하여 수화성 분말을 제조한다.Compound 3 40%, diatomaceous earth 15%, clay 15%, white carbon 25%, sodium dinaphthylmethane disulfonate 2% and sodium lignin sulfonate 3% were uniformly mixed and ground to prepare a hydrated powder.
[제형예 3] : 분진Formulation Example 3 Dust
화합물 1 2%, 규조토 5% 및 점토 93%을 균일하게 혼합 분쇄하여 분진을 제조한다.2% of compound 1, 5% of diatomaceous earth, and 93% of clay were mixed and ground uniformly to prepare dust.
[제형예 4] : 과립Formulation Example 4 Granules
화합물 7 5%, 라우릴 알콜 황산 에스테르 소듐염 2%, 소듐 리그닌 술포네이트 5%, 카르복시메틸 셀룰로스 2% 및 점토 86%을 균일하게 혼합 분쇄한다. 이어서, 생성 혼합물 100중량부를 물 20중량부에 가하고 혼련하여 압출형 입화기를 통해 14~24메쉬의 과립으로 성형한 후 건조시켜 과립을 형성한다.5% compound 7, 2% lauryl alcohol sulfate ester sodium salt, 5% sodium lignin sulfonate, 2% carboxymethyl cellulose and 86% clay are mixed and ground uniformly. Subsequently, 100 parts by weight of the resulting mixture is added to 20 parts by weight of water and kneaded to form granules of 14 to 24 mesh through an extruder granulator, followed by drying to form granules.
본 발명에 따른 트리아졸 유도체는 목화 진딧물, 복숭아혹 진딧물, 양배추 가루 진딧물 등의 진딧물류; 벼멸구, 흰등멸구, 애멸구 등의 멸구류; 끝동매미충, 말매미충 등의 매미충류; 귤가루이 등의 가루이류; 뽕나무 깍지벌레, 노린재 등의 노린재목 해충; 배추 좀나방, 리마콩 거세미나방, 담배 거세미나방 등의 나비목 해충; 집파리, 모기등의 파리목 해충; 벼뿌리 바구미, 콩 바구미, 오이 잎벌레 등의 딱정벌레목 해충; 바퀴, 스팀플라이 등의 바퀴류; 및 점박이 응애, 칸자와 응애, 귤응애 등의 응애류를 방제하는데 유효하다.Triazole derivatives according to the present invention include aphids such as cotton aphid, peach hump aphid, cabbage powder aphid; Extinct species such as rice bulbs, white bulbs, and larvae; Cicada larvae such as cicada larva and horse cicada; Flours such as tangerine powder; Stink bugs such as mulberry bark insects and stink bugs; Lepidoptera pests such as Chinese cabbage moth, lima bean castor moth, and tobacco castor moth; Flyfly pests such as houseflies and mosquitoes; Coleopteran pests such as rice root weevil, bean weevil, cucumber leaf beetle; Wheels such as wheels and steam plies; And spots are effective in controlling mites such as mites, Kanza mites, and tangerine mites.
특히, 본 발명에 따른 살충제는 목화 진딧물, 복숭아혹 진딧물, 싸리수염 진딧물, 양배추 가루 진딧물 등의 진딧물류; 귤가루이, 고구마 가루이 등의 가루이류; 뽕나무 깍지벌레 등의 노린재목 해충; 노랑총채벌레 등의 총채벌레류; 및 점박이 응애, 칸자와 응애, 귤응애 등의 응애류를 방제하는데 있어서 매우 우수한 효과를 나타낸다.In particular, the pesticides according to the present invention include aphids such as cotton aphid, peach hump aphid, hydrangea aphid, cabbage powder aphid; Flours such as tangerine powder and sweet potato powder; Stink bugs such as mulberry bark; Thrips such as yellow thrips; And spots exhibit very excellent effects in controlling mites such as mites, Kanza mites and tangerine mites.
본 발명에 따른 화합물의 효과는 하기 실험예에서 기술된다. 또한, 하기 화합물은 비교용 화학약품으로 사용된다. 비교용 화학약품 A~C는 리서치 디스클로져 RD 278004에 기재된 화합물이며 상기와 같은 제제에 의해 사용되는 한편, 비교용 화학약품 D 및 E는 진딧물 방제용 시판물이다.The effects of the compounds according to the invention are described in the following experimental examples. In addition, the following compounds are used as comparative chemicals. Comparative Chemicals A-C are the compounds described in Research Disclosure RD 278004 and are used by such formulations, while Comparative Chemicals D and E are commercially available products for controlling aphids.
비교용 화학약품 A : 3-(2-클로로페닐)-5-(2-클로로피리딘-3-일)-1-메틸-1H-1,2,4-트리아졸Comparative Chemicals A: 3- (2-Chlorophenyl) -5- (2-chloropyridin-3-yl) -1-methyl-1H-1,2,4-triazole
비교용 화학약품 B : 3-(2-클로로페닐)-5-(6-클로로피리딘-3-일)-1-메틸-1H-1,2,4-트리아졸Comparative Chemicals B: 3- (2-Chlorophenyl) -5- (6-chloropyridin-3-yl) -1-methyl-1H-1,2,4-triazole
비교용 화학약품 C : 3-(2-클로로-4-플루오로페닐)-5-(6-클로로피리딘-3-일)-1-메틸-1H-1,2,4-트리아졸Comparative Chemical C: 3- (2-chloro-4-fluorophenyl) -5- (6-chloropyridin-3-yl) -1-methyl-1H-1,2,4-triazole
비교용 화학약품 D : 메토밀의 45% 수화성 분말Comparative Chemical D: 45% Hydrating Powder of Metomil
비교용 화학약품 E : 에티오펜카르브의 50% 에멀션Comparative Chemical E: 50% Emulsion of Ethiophene Carb
[시험예 1] : 침액법을 통한 살충성 시험Test Example 1: Insecticidal test through immersion method
제형예 2에 따라 제조된 수화성 분말을 물로 희석하여 활성성분의 농도가 0.8ppm 또는 0.16ppm이 되도록 한다. 생성되는 희석 수화성 분말에 미리 목화 진딧물 유충으로 접종시킨 오이 묘종을 침액시킨 후 공기중 건조처리한다. 처리후, 오이 묘종을 25℃의 항온실에 3일간 둔 다음 죽은 유층수를 계수하여 폐사율을 계산한다. 2회 연속으로 시험을 반복한다. 결과를 표 2에 나타낸다.The water-soluble powder prepared according to Formulation Example 2 is diluted with water so that the concentration of the active ingredient is 0.8 ppm or 0.16 ppm. Cucumber seedlings previously inoculated with the resulting aphid larvae are immersed in the resulting dilute hydrating powder and then dried in air. After treatment, cucumber seedlings are placed in a constant temperature room at 25 ° C. for 3 days, and the dead seawater is counted to calculate mortality. Repeat the test two times in succession. The results are shown in Table 2.
[표 2]TABLE 2
[시험예 2] : 주입법을 통한 살충성 시험Test Example 2: Insecticidal test through injection method
제형예 2에 따라 제조된 수화성 분말을 물로 희석하여 활성성분의 농도가 0.8ppm 또는 0.16ppm이 되도록 한다. 생성되는 희석 수화성 분말을 미리 목화 진딧물 유충으로 접종시킨 오이 묘종을 함유하는 포트에 주입한다. 주입후,오이 묘종을 25℃의 항온실에 3일간 둔 다음 죽은 유충수를 계수하여 폐사율을 계산한다. 2회 연속으로 시험을 반복한다. 결과를 표 3에 나타낸다.The water-soluble powder prepared according to Formulation Example 2 is diluted with water so that the concentration of the active ingredient is 0.8 ppm or 0.16 ppm. The resulting dilute hydrable powder is injected into a pot containing cucumber seedlings previously inoculated with cotton aphid larvae. After infusion, cucumber seedlings are placed in a constant temperature room at 25 ° C. for 3 days, and dead larvae are counted to calculate mortality. Repeat the test two times in succession. The results are shown in Table 3.
[표 3]TABLE 3
[시험예 3] : 토양 개질처리법을 통한 체계이동 조절 시험[Test Example 3]: System movement control test through soil reforming
제형예 4에 따라 제조된 과립 (0.5kg / 10아르)을 미리 진딧물 유충으로 접종시킨 포트에 심은 오이 묘종 뿌리에 살포한다. 처리후, 포트를 온실에 두고, 생존하는 성충 및 유충수를 7일 마다 계수한다. 3회 연속으로 시험을 반복한다. 결과를 표 4에 나타낸다.Granules prepared according to Formulation Example 4 (0.5 kg / 10 are) are sprayed on the roots of cucumber seedlings planted in pots previously inoculated with aphid larvae. After treatment, the pots are placed in a greenhouse and surviving adult and larvae are counted every 7 days. The test is repeated three times in succession. The results are shown in Table 4.
[표 4]TABLE 4
[시험예4] : 줄기 및 잎에 분무하는 방법을 통한 체계이동 조절 시험[Test Example 4]: System movement control test by spraying on stems and leaves
제형예 2에 따라 제조된 수화성 분말을 물로 희석하여 활성성분의 농도가 100ppm로 되도록 한다. 생성되는 희석 수화성 분말을 배면상에 분무시키지 않고 미리 진딧물 유충으로 배면이 접종된 포트에 심은 오이 표종의 잎의 앞면에만 분무한다. 처리후, 포트를 온실에 두고, 배면에서 생존하는 성충 및 유충의 수를 5일마다 계수한다. 3회 연속으로 시험을 반복한다. 결과를 표 5에 나타낸다.The water-soluble powder prepared according to Formulation Example 2 is diluted with water so that the concentration of the active ingredient is 100 ppm. The resulting dilute hydrating powder is sprayed only on the front side of the leaves of cucumber seedlings planted in a pot previously inoculated with aphid larvae without spraying on the back. After treatment, the pot is placed in a greenhouse and the number of adult and larvae surviving on the back is counted every 5 days. The test is repeated three times in succession. The results are shown in Table 5.
[표 5]TABLE 5
Claims (7)
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| EP1113004A3 (en) * | 1997-04-24 | 2001-07-18 | Dow Agrosciences LLC | Intermediates for producing 3-(substituted phenyl)-5-(thienyl or furyl)-1,2,4-triazole compounds |
| JP4306806B2 (en) | 1997-04-24 | 2009-08-05 | ダウ・アグロサイエンス・エル・エル・シー | Pest control 3- (substituted phenyl) -5- (thienyl or furyl) -1,2,4-triazole |
| US6413997B1 (en) | 1998-10-23 | 2002-07-02 | Dow Agrosciences Llc | 3-(substituted phenyl)-5-(substituted heterocyclyl)-1,2,4-triazole compounds |
| CO5221041A1 (en) | 1998-10-23 | 2002-11-28 | Dow Agrosciences Llc | COMPOUNDS OF 3- (REPLACED PHENYL) -5-TIENIL-1.2.4- TRIAZOL WITH ACTIVITY AGAINST WHITE FLY AND INSECTICIATED COMPOSITIONS CONTAINING IT |
| EP1123287B1 (en) * | 1998-10-23 | 2003-07-30 | Dow AgroSciences LLC | Insecticidal 3- (substituted pyridyl) -1, 2, 4-triazoles |
| DE69936592T2 (en) | 1998-10-23 | 2008-04-30 | Dow Agrosciences Llc, Indianapolis | PROCESS FOR PREPARING 3- (SUBSTITUTED PHENYL) -5-THIENYL (OR FURYL) - 1,2,4-TRIAZOLENE AND THE INTERMEDIATES USED IN THE PROCESS |
| JP4299139B2 (en) * | 2001-12-18 | 2009-07-22 | メルク エンド カムパニー インコーポレーテッド | Heteroaryl-substituted triazole modulators of metabotropic glutamate receptor-5 |
| JP4881725B2 (en) * | 2003-04-09 | 2012-02-22 | エクセリクシス， インク． | TIE-2 modulator and usage |
| WO2005004818A2 (en) * | 2003-07-09 | 2005-01-20 | Imclone Systems Incorporated | Heterocyclic compounds and their use as anticancer agents |
| RU2476428C1 (en) * | 2011-09-01 | 2013-02-27 | Государственное образовательное учреждение высшего профессионального образования "Южно-Российский государственный технический университет (Новочеркасский политехнический институт)" | Method of producing 5-amino-3-aminomethyl-1,2,4-triazole dihydrochloride |
| MX362102B (en) * | 2012-07-25 | 2019-01-04 | Fujiyakuhin Co Ltd | Method of producing 4-[5-(pyridin-4-yl)-1h-1,2,4-triazole-3-yl]py ridin-2-carbonitrile, and intermediary thereof. |
| US9573936B2 (en) * | 2015-05-20 | 2017-02-21 | Amgen Inc. | Triazole agonists of the APJ receptor |
| JP2017110003A (en) * | 2015-12-16 | 2017-06-22 | 日本曹達株式会社 | Diaryltriazole compound and noxious organism-controlling agent |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7112373A (en) * | 1970-09-25 | 1972-03-28 | ||
| EP0036711B1 (en) * | 1980-03-22 | 1985-12-04 | Fbc Limited | Pesticidal heterocyclic compounds, processes for preparing them, compositions containing them, and their use |
| AR241530A1 (en) * | 1984-12-21 | 1992-08-31 | Ciba Geigy A G Cesionaria De F | Triazole derivates, their preparation and their use as pesticides |
| JPS62149673A (en) * | 1985-09-05 | 1987-07-03 | Sumitomo Chem Co Ltd | Pyridine derivative, production thereof and plant blight controlling agent containing said derivative as active component |
| DE3631511A1 (en) * | 1986-09-12 | 1988-03-24 | Schering Ag | 5-Halo-1,2,4-triazoles, their preparation, and their use as acaricides and insecticides |
-
1992
- 1992-03-04 JP JP08141292A patent/JP3217846B2/en not_active Expired - Fee Related
- 1992-10-06 US US07/956,980 patent/US5284860A/en not_active Expired - Fee Related
-
1993
- 1993-02-23 EP EP93301325A patent/EP0559363B1/en not_active Expired - Lifetime
- 1993-02-23 ES ES93301325T patent/ES2210234T3/en not_active Expired - Lifetime
- 1993-02-23 DE DE69333264T patent/DE69333264D1/en not_active Expired - Lifetime
- 1993-02-26 KR KR1019930002838A patent/KR100229256B1/en not_active IP Right Cessation
- 1993-03-03 CN CN93103590A patent/CN1039905C/en not_active Expired - Fee Related
- 1993-03-03 RU RU93004658A patent/RU2101282C1/en not_active IP Right Cessation
- 1993-03-03 BR BR9300732A patent/BR9300732A/en not_active IP Right Cessation
- 1993-06-03 EG EG12993A patent/EG20363A/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CN1078467A (en) | 1993-11-17 |
| KR930019659A (en) | 1993-10-18 |
| EP0559363B1 (en) | 2003-10-29 |
| JPH05247029A (en) | 1993-09-24 |
| BR9300732A (en) | 1993-09-08 |
| RU2101282C1 (en) | 1998-01-10 |
| US5284860A (en) | 1994-02-08 |
| JP3217846B2 (en) | 2001-10-15 |
| EP0559363A1 (en) | 1993-09-08 |
| EG20363A (en) | 1999-01-31 |
| DE69333264D1 (en) | 2003-12-04 |
| CN1039905C (en) | 1998-09-23 |
| ES2210234T3 (en) | 2004-07-01 |
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